Fe 3 O 4 @SiO 2-CeCl 3 catalyzed chemoselective synthesis of functionalized 3-substituted-1,5-benzodiazepines via one-pot multicomponent and domino reactions has been developed. During the one-pot synthesis process, one new cycle and four new bonds (one CC , two C-N and one C=C) were constructed by the nucleophilic addition and eliminate reaction (dehydration etc.) process, intramolecular proton transfer and cyclization process. The major advantages of the present method are good to excellent yields, shorter reaction time, simple experimental procedure, easy work up, mild reaction conditions, recyclability of the catalyst and ability to tolerate a variety of functional groups which gives economical as well as ecological rewards. K E Y W O R D S 3-substituted-1,5-benzodiazepines, catalysis, domino reaction, Fe 3 O 4 @SiO 2-CeCl 3 , one-pot multicomponent